We now discuss two related notions:
When we consider a conserved quantity such as energy, momentum, or charge, these two notions stand in a one-to-one relationship. In general, though, these two notions are not equivalent.
In particular, consider equation 6.32, which is restated here:
| dE = −P dV + T dS + advection (15.1) |
Although officially dE represents the change in energy in the interior of the region, we are free to interpret it as the flow of energy across the boundary. This works because E is a conserved quantity.
The advection term is explicitly a boundary-flow term.
It is extremely tempting to interpret the two remaining terms as boundary-flow terms also … but this is not correct!
Officially PdV describes a property of the interior of the region. Ditto for TdS. Neither of these can be converted to a boundary-flow notion, because neither of them represents a conserved quantity. In particular, PdV energy can turn into TdS energy entirely within the interior of the region, without any boundary being involved.
Let’s be clear: boundary-flow ideas are elegant, powerful, and widely useful. Please don’t think I am saying anything bad about boundary-flow ideas. I am just saying that the PdV and TdS terms do not represent flows across a boundary.
Misinterpreting TdS as a boundary term is a ghastly mistake. It is more-or-less tantamount to assuming that heat is a conserved quantity unto itself. It would set science back over 200 years, back to the “caloric” theory.
Once these mistakes have been pointed out, they seem obvious, easy to spot, and easy to avoid. But beware: mistakes of this type are extremely prevalent in introductory-level thermodynamics books.